Process for breaking petroleum emulsions employing gluconic acid salts of oxyalkylated amine-modified thermoplastic phenol-aldehyde resins



United States Patent PROCESS FOR BREAKING PETROLEUM EMUL- SIONS EMPLOYING GLUCONIC ACID SALTS OF OXYALKYLATED ANlINE-MODIFIED THERMO- PLASTIC PHENOL-ALDEHYDE RESINS Melvin De Groote, University City, M0,, assignor to Petrolite Corporation, Wilmington, DeL, a corporation of Delaware 1 No Drawing. Application January 26, 1953,

, Serial No. 333,389

36 Claims. (Cl. 252-441) The present invention is a continuation-in-part of my five co-pending applications, Serial No. 288,745, filed May 19, 1952, now abandoned; Serial No. 296,086, filed June 27, 1952, now U. S. Patent 2,679,487; Serial No. 301,806, filed July 30, 1952, now U. S. Patent 2,743,254; Serial No. 310,554, filed September 19, 1952, now U. S. Patent 2,695,890, and Serial No. 329,485, filed January 2, 1953.

My invention provides an economical and rapid processfor resolving petroleum emulsions of the water-in-oil type, that are commonly referred to as cut oil, roily-oil, emulsified oil, etc., and which comprise fine droplets of naturally-occurring waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion.

It also provides an economical and rapid process for separating emulsions which have been prepared under controlled conditions from mineral oil, such as crude oil and relatively soft waters or weak brines. Controlled emulsification and subsequent demulsification under the conditions just mentioned are of significant value in removing impurities, particularly inorganic salts, from pipeline oil.

My aforementioned co-pending application, Serial No. 310,554, filed September 19, 1952, is concerned with a process for breaking petroleum emulsions of the waterin-oil type characterized by subjecting the emulsion to the action of a demulsifier including certain products obtained by the oxyalkylation of condensates of phenolaldehyde resins, basic hydroxylated polyamines and form aldehyde therein described.

My present invention is concerned with demulsification which involves the use of the aforementioned amino resin condensate in the form of a gluconic acid salt, i. e., a form in which all the basic nitrogen atoms are neutralized with gluconic acid, i. e., converted into the salt of gluconic acid.

Needless to say, all that is required is to prepare the amine resin condensates in the manner described in the two aforementioned co-pending applications, and then neutralize With gluconic acid which, for practical purposes is as simple as analogous inorganic reactions.

As far as the use of the herein described products goes for purpose of resolution of petroleum emulsions of the Water-in-oil type, I particularly prefer to use the gluconic acid salt of those members which have sufficient hydrophile character to meet at least the test as set forth in U. S. Patent No. 2,499,368, dated March 7, 1950, to De Groote et al. In said patent such test for emulsification using a water-insoluble solvent, generally xylene, is described .as an index of surface activity.

The present invention involves the surface-activity of the gluconic acid salts, i. e., either where only one basic amino nitrogen atom .is neutralized or where all basic amino nitrogen atoms are neutralized. Such gluconic acid salts may not necessarily be xylene-soluble. If such compounds are not xylene-soluble the obvious chemical equivalent or equivalent chemical test can be made by simply using some suitable solvent, preferably a water- 2,771,448 Patented Nov. 20, 1956 2 soluble solvent such as ethylene glycol diethyle'ther, or a low molal alcohol, or a mixture to dissolve the appropriate product being examined and then mixwith the.

equal weight of xylene, followed by addition of Water. Such test is obviously the same for the reason that there will be two phases on vigorous shaking and surface activity makes its presencemanifest. It is understood the reference in the hereto appended claims as to the use of xylene in the emulsification test. includes such obvious variant.

For convenience, what is said hereinafter will be dipreparation of the herein described amine-modified resins;

Part 4 is concerned with reactions involving the resin, the hydroxylated polyamine, and formaldehyde to produce specific products or compounds which are then subjected to oxyalkylation;

Part 5 is concerned with the oxyalkylation of the products described in Part 4 preceding;

Part 6.is concerned with the conversion of the basic oxyalkylated derivatives described in Part 5, preeedin in the corresponding salt of giuconic'acid;

Part 7 is concerned with the resolution of petroleum emulsions of the ,water-in-oil type by means of the previously described chemical compounds or reaction products in the form of gluconic acid salts.

PART 1 R i R in which R represents an aliphatic hydrocarbon substituent generally having 4 and notover 18 carbon atoms but most preferably not over 14 carbon atoms, and n generally is a small whole number varying from 1 to 4. In the resin structure it is shown as being derivedfrom formaldehyde although obviously other aldehydes are equally satisfactory. The amine residue in the above structure is derived from .a hydroxylated basic ,polyamine and usually a strongly basic polyamine having at ElCEtSt one secondary amino radical and free from any primary amino radical, any substituted imidazoline radical and any substituted tetrahydropyrimidine radical, and may be 1 indicated thus:

Lin which R representsany appropriate hydrocarbon radical, such as an alkyl, alicyclic, arylalkyl radical, etc, with Such formula radical, etc; Such hydroxylated radical need not be limited to a single hydroxy group as in the case of an alkanol radical but may include 2 or more hydroxyl groups, such as a glycerol derivative or, in essence, a dihydroxy propyl n' 7 Actually, what has been depicted in the formula above is only an over-simplified exemplification of that part of the polyamine which has the reactive secondary amino group. Actually, a more complete illustration is obtained by reference to oxalkylated derivatives obtained by the oxyethylation or oxypropylation, for example, of substituted polyalkylene amines of the following structure:

R v R N.o.H,...(o,.H,,.N.D),N

- R V 7 RI! in which R has its prior significance, R" represents a hydrogen atom or radical R, D is a hydrogen atom or an alkyl group, n represents the numerals 1 to 10, and x represents a small whole number varying from 1 to 7 but generally from 1 to 3, with the proviso that the other previously stated requirements are met. See U. S. Patent No. 2,250,176, dated July 22, 1941, to Blair. Reaction with an alkylene oxide, such asethylene oxide or propylene oxide must of course be sure that the derivative so obtained still has at least one'secondary amino hydrogen group, all of which willbe illustrated by numerous examples subsequently.

See also U. S. Patent No. 2,362,464, dated November 14, 1944, to Britton et al, which describes alkylene di- :that the secondary amino, radical shall notbe directly joined to an aryl radical or vacyl radical or some other negative radical. Needless to say, what has been stated above in regard to the groups'atta'ched to nitrogen is not intended to exclude an oxygen-interrupted carbon atom linkage or a ring linkage as in the instance of compounds obtained by converting. an N-aminoalkylmorpholine of the formula oEn- OH:

wherein n is a whole'number from 2 to 12 inclusive, and thetnitrogen atoms' are separated by at least two carbon atoms, into a secondary amine by means of an alkylene oxide,-such as ethylene oxide, propylene oxide, or glycide, so as to yield a compound such as 1 w e 2 o N-Chin-N OHrCz CZHLOH The introduction of two such hydroxylated polyamine radicals into a comparatively small resin molecule, for instance, one having 3 to 6 phenolic nuclei as specified, alters the product in a number of ways. In the first place, a basic nitrogen atom, of course, adds a hydrophile eflect;

in the second place, depending on the size of the radical The resins employed as raw materials in the instant procedure are characterized by the presenceof an aliphatic radcial in the ortho or para position, i. e., the phenols themselves are difunctional phenols.

The resins herein employed contain only two terminal groups which are reactive to formaldehyde, i. e., they are difunctional from the standpoint of methylol-forming reactions. As is well known, although one may start with difunctional phenols, and depending onrthe procedure employed, one may obtain cross-linking which in:

dicates that one or more of the phenolic nuclei have been converted from a difunctional radical to a trifunctional radical, or in terms of the resin, the molecule as a whole has a methylol-formingreactivity greater than 2. Such shift can take place after the resin has been formed or during resin formation. Briefly, an example is simply where an alkyl radical, such as methyl, ethyl, propyl, butyl, or the like, shifts from an ortho position to a meta position, or from a para position to a meta position. For instance, in the case of phenol-aldehyde varnish resins, one can prepare at least some in which the resins, instead of having only two points of reaction can have three, and

The resins herein employed are soluble in a n0n-oxy-.

genated hydrocarbon solvent, such as benzene or xylene. The resins herein employed as raw materials must be comparatively low molal products having on the average 3 to 6 nuclei per resin molecule.

The condensation products here obtained, whether in the form of the free base or the salt, do not go over to the insoluble stage on heating. The condensation product obtained according to the present invention is heat-stable and, in fact, one of its outstanding qualities is that it can be subjected to oxyalkylation, particularly oxyethylation or oxypropylation, under conventional conditions, i. e., presence of an alkaline catalyst, for example, but in any event at a temperature above C. without becoming an insoluble mass.

What has been said previously in regard to heat stability, particularly when employed as a reactant for preparation of derivatives, is still important from the stand-' point of manufacture of the condensation products them:

selves insofar that in the condensation process employed in preparing the compounds described subsequently in detail, there is no objection to the employing of a temperhave manufacturing procedure which will allow reactions to take place at the interface of the two immiscible liquids, to wit, the formaldehyde solution and the resin solution, on the assumption that generally the amine will dissolve in one phase or the other. kind herein described will begin at least at comparatively low temperatures, for instance, 30 C., 40 C., or 50 C., yet the reaction does not go to completion except by the use of the higher temperatures. The use of higher tem- V peratures means, of course, that the condensation product In the present procedure the Although reactions of the no l obtained at the end of the reaction must not be heat-reactive. Of course, one can add an oxygenated solvent such as alcohol, dioxan e, variousethe'rs'of glycols, or the like, and produce a homogeneous phase. If this latter procedure is employed in preparin the herein described condensations it is purely a matter of convenience, but whether it is or not, ultimately the temperature-' must still pass within the zone indicated elsewhere, i. e.,- somewhere above the boiling point of water unless some obvious equivalent procedure is used;

Any reference, as in the hereto appended claims, to the procedure employed in the process is not intended to limit the method or order in which the: reactants are added, commingled or reacted. The procedure has been referred to as a condensation process for obvious reasons. As pointed out elsewhere it is my preference to dissolve the resin in a suitable solvent, add the amine,

and then add the formaldehyde'as a 37% solution. However, all three reactants can be added in any order. I am inclined to believe that in thepresence of a basic catalyst, such as the amine employed, that theformalde hyde produces methylol groups attached to the phenolic nuclei which, in turn, react with the' amine. It would be immaterial, of course, if the formaldehyde reacted with the amine so as to introduce a methylol group attached to nitrogen which, in turn, would react with the resin molecule. Also, it would be immaterial if both types of compounds were formed which reacted with each other with the evolution of a'mole of formaldehyde available for further reaction. Furthermore, a reaction could take place in which three different molecules are simultaneously involved although, for theoretical reasons, that is less likely. Whatis said hereinin'thisrespect is simply by way of explanation to avoid any limitation in regard to the appended claims.

PART 2 It is well known that one can readily purchase on the open market, or prepare fusible, organic solvent-soluble,

water-insoluble resin polymers of a composition approximated in an idealized form by the formula In the above formula n represents a small Whole number varying from 1 to 6, 7 or 8, or more, up to" probably 10 or 12 units, particularly when the resin is subjected to heating under a vacuum as described in the literature. A limited sub-genus is in the instance of low molecular weight polymers where the total number of phenol nuclei varies from 3 to 6, i. e., n varies from 1 to 4; R represents an aliphatic hydrocarbon substit'uent, generally an alkyl radical having from 4 to 14 carbon atoms; such as a butyl, amyl, hexyl, decyl or dodecyl radical. Where the divalent bridge radical is shown as being derived from formaldehyde it may, of course, be derived from any other reactive aldehyde having 8 carbon atoms or less.

The resin herein employed as raw materials must be soluble in a nonoxygenated solvent, such as benzene or xylene. This presents no problem insofar that all that is required is to make a solubility test on commercially available resins, or else prepare resins which are xylene or benzene-soluble as described in aforementioned U. S. Patent No. 2,499,365, or in U. S. Patent No. 2,499,368 dated March 7, 1950, to De Groote and Keiser.

If one selected a resin of the kind just described previously and reacted approximately one mole of the resin with two moles of formaldehyde and two molesof a basic non-hydroxylated secondary amine as specified, following the same idealized over-simplification previously referred to, the resultant product might be illustrated thus:

The'basic'polyamine may be designated thus:

R HN/ R! subject to what has been said previously as to the presence of atleast one amine radical in' at least one occurrence of R with the proviso, as previously stated, that the amine radical be other than a primary amine radical, a substituted imidazoline radical or a substituted tetrahydropyrimidine radical, with'the proviso'thattherein-11st be present at least one hydroxyl radical as part ofat least one of the occurrence of R. However, if one attempts to incorporate into theformula I in which the various characters have the same significance as in initial presentation of this formula, then one be'- comesinvolved in added difiiculties in-presentinganover all picture. Thus, for sake of simplicity, the hydroxylated polyamine will be depicted as In conducting reactions of this kind one does not necessarily obtain a=hunclred percent yield for obvious reasons.

Certain side reactions may takeplace. For instance, 2 moles of amine may combine with one mole of the aldehyde, or only onemole of the amine may combine with the resin molecule, or even to a very slight extent, if at i all, 2 resin units may combine without any amine in the reaction products, as indicatedinthe following formulas:

As has been pointed out previously, as far as the resin unit goes one can use a mole of aldehyde other than form- I aldehyde, such as acetaldehyde, pr'opionaldehyde or butyr-. aldehyde. The resin unit may be-exemplified thus:

in which R' is the divalent radical obtained from the .viously mentioned U. S. Patent 2,499,368.

particular aldehyde employed to form the resin. For reasons which are obvious the condensation product obtained appears to be described best in terms of the method of manufacture. q

As previously stated the preparation of resins, the kind herein employed as reactants, is well known. See pre- Resins can be made using an acid catalyst or basic catalyst or a catalyst having neither acid nor basic properties in the ordinary sense or without any catalyst at all. It is preferable that the resins employed be substantially neutral. In otherwords, if prepared by using a strong acid as a catalyst, such strong acid should be neutralized. Similarly, if a strong base is used as a catalyst it is preferable that the base be neutralized although I have found that sometimes the reaction described proceeded more rapidly in the: presence of a small amount of a free base. The amount may be a small as a 200th of a percent and as much as a few lths of a percent.. Sometimes moderate increase in caustic soda and caustic potash may be used. However, the most desirable procedure in practically every case is to have the resin neutral.

In preparing resins one does not get a single polymer, i.' e.,;one having just 3 units, or just 4 units, or just 5 units or'just 6 units, etc. It is usually a mixture; for instance, one approximating 4 phenolic nuclei will have some trimer and pentamer present. Thus, the molecular weight may be such that it corersponds to a fractional value for n as, for example, 3.5, 4.5 or 5.2.

In the actual manufacture of the resins-I found no reason for using other than those which are lowest in price and most readily available commercially. For purposesof convenience suitable resins are characterized in the following table:

TABLE I M01. wt Ex- I R of resin ample R Position derived 1 molecule number of R from- (based 0 on n+2) Phenyl Para 3.5 992.5

Tertiary butyl do 3. 5 882. 5 Secondary butyl- Ortho 3. 5 882. 5 Cyclo-hexyl Para- 3. 5 1, 025. 5 Tertiary amyl 3. 5 959. 5 Mixed secondary 3. 5 805. 5

and tertiary amyl.

Tertiary amy1 do 3. 5 1, 022. 5 Nonyl do 3. 5 1, 330. 5 Tertiary butyl 3. 5 1, 071. 5 Tertiary amyl 3. 5 1, 148. 5 Non 3. 5 1, 456. 5 Tertiary butyl 3. 5 1, 008. 5

Tertiary amyl 3. 5 1, 085. 5 Nonyl 3. 5 1, 393. 5 Tertiary butyl 4. 2 996. 6

4. 2 1, 083. 4 ony 4. 2 1, 430. 6 Tertiary butyl. 4. 8 1, 094. 4 Tertiary amyl 4. 8 1, 189. 6 N 1 4. a 1, 570. 4 l. 5 g l. 5 1. 5 653. 0 1. 5 688. 0

2.0 692. 0 Hexy 2. 0 748. Cycle-hexyl 2. 0 740. 0

8 PART 3 As hasbeen pointed out, the amine herein employed as a reactant is a hydroxylated basic polyamine and preferably a strongly basic polyamine having at least one secondary amino radical, free from primary amino groups, free from substituted imidazoline groups, and free from substituted tetrahydropyrimidine groups, in which the hydrocarbon radicals present whether monovalent or divalent are alkyl, alkycyclic, arylalkyl, or heterocyclic in character, subject of course to the inclusion of a hydroxyl group attached to a carbon atom which in turn is part of a monovalent or divalent radical.

Previous reference has been made to a number ofpolyamines which are satisfactory for use as reactants in the instant condensation procedure. They can be obtained by hydroxya'lkylation-of low cost polyamines. The cheapest amines available are polyethylene amines and polypropylene amines. In the case of the polyethylene amines there may be as many as 5, 6 or 7 nitrogen atoms. Such amines are susceptible to terminal alkylation or the equivalent, i. e., reactions which convert the terminal primary amino group or groups into a secondary or tertiary amine radical. In the case of polyamines having at least 3 nitrogen atoms or more, both terminal groups could be converted into tertiary groups, or one terminal group could be converted into a tertiary group and the other into a secondary amine group. In the same way, the polyamines can'be subjected to hydroxyalkylation by reaction with ethylene oxide, propylene oxide, glycide, etc. In some instances, depending on the structure, both types of reaction may be employed, i. e., one type to introduce a hydroxy ethyl group, for example, and another type to introduce a methyl or ethyl radical. 1

By way of example the following formulas are included. It will be noted they include such polyamines which, instead of being obtained from ethylene dichloride, propylene dichloride or the like, are obtained from dichloroethyl ethers in which the divalent radical has a carbon atom chain interrupted by an oxygen atom:

HO C2114 NC zHlN C 2H4N C zHiN C 1H4N H H H HO 0 H; 02114011 1100111. C2H4OH NolniNoimNoznmoimN n i H n CH3 CH3 HOCZHJ ene oxide, such as ethylene oxide, propylene, oxide or glycide. I

What has been said previeuslymay be illustrated by reactions involving a secondary alkyl amine, or a second-.-

ary alicyclic amine, such as dibutylamine, dibenzylamine, dicyclohexylamine, or mixed amines with an imine so as to introduce a primary amino group which can be re-.

acted with an alkylene oxide followed by reaction with an imine and then the use of an alkylene oxide again. Similarly, one can start with a primary amine and introduce two moles of an alkylene oxide so as to have a comamine plus analkylene oxide plus an alkylene imine and.

plus the second introduction of an alkylene'oxide, can be applied to a variety of primary amines. Inthe case of primary amines one can either employ two moles of an alkylene oxide so as to convert both amino hydrogen atoms into an alkanol group, or the equiVa-lent; or else the primary amine can be convertedinto a secondary amine by the alkylation reaction. tain a series of primary amines and corresponding secondary amines which are characterized by the fact that such amines include groups having repetitious ether linkages and thus introduce a definite hydrophile effect by virtue of the ether linkage. Suitable polyether. amines susceptible to conversion in the manner described include those of the formula in which 25 is a small whole number having a value of 1 or more, and may be as much as 10 or 12; n fs an integer having a value of 2 to 4, inclusive; m represents the numeral 1 to 2; and 111 represents a number to l, with the proviso that the sum of m plus-m equals 2; and R has its prior significance, particularly as a hydrocarbon radical. v

The preparation of such amines has been described in the literature and particularly in two United States patents, to wit, U. S. Nos. 2,325,514, dated July 27,.1943,.to Hester, and 2,355,337 dated August 8, l944, to Spence.

The latter patent describes typical haloalkyl others suchas v c1130 02B4C1' pm (1132 on. CHCH2O otmo 02mm Such haloalkyl ethers can react withammonia, or with a primary amine such as methylamine, ethylamine, cyclo- Other similar secondary monoamines equally suitable for such conversion reactions in order to yield appropri ate secondary amines, are those of the composition NB RO(CH2)B/ as described in U. s. Patent bin-2,375,659, dated May- 8,

1945, to Jones et al. In the above formula R may be methyl, ethyl, propyl, amyl, octyl,;etc.

In any event, one .can ob- Other suitable secondary amines which can be con verted into appropriate polyamines can be obtained from products which are sold in the open market, such as may be obtained by alkylation of cyclohexylmethylamine or the alkylation of similar primary amines, or for that matter, amines of the kind described in U. S. Patent No.

2,482,546, dated September ZO, 1949, to Kaszuba, provided there is no negative group or halogen attached to the phenolic nucleus. Examples include the following: beta-phenoxyethylamine, gamma phenoxypropylamine, beta-phenoxy-alpha-methylethylamine, and beta-phenoxypropylamine.

Other secondary monoamines suitablefor conversion into polyamines are the kind described in British Patent No. 456,517, and may be illustrated by In light of the various examples of polyamines which have been used for illustration it may be well to refer again to the fact that previously the amine was shown as with the statement that such presentation is an oversimplification. It was pointed out that at least one occurrence of R must include a secondary amino radical of the kind specified. Actually, if the piolyamine radical contains two or more secondary amino groups the amine may be reactive at two different. positions and thus the same amine may yield compounds in which R and R are dissimilar.

CH3 CH: H V /NpropyleneNpropyleneN= H C2H4OH CH: CH;

In the first of the two above formulas if the reaction involves a terminal amino hydrogen obviously the radicals attached to the nitrogen atom, which in turn combines with the methylene bridge, would. be. different than if the reaction took place at the intermediate secondary amino radicaldas differentiated from the terminal group. Again, referring to the second formula above, although a terminal amino radical is not involved it is obvious again that one could obtain two diiferent structures for the radicals attached to the nitrogen atom-united to the 'tained due to such multiplicity of reactive radicals.

methylene bridge, depending on whether the reaction took place at either" one of the two outer secondary amino groups, or at the central secondary amino group. If there are two points of reactivity towards formaldehyde 'as illustrated by the above examples it is obvious that one might get a mixture in which in part the reaction took place at one point and in part at another point.

Certain hydroxylated polyamines which may be employed and which illustrate the-appropriate type of reactant used for the instant condensation reaction maybe illustrated by the following-additional examples: t

OH: I h

N omo'fN-QHQOHPOH nooatcamn cngomanncmcmon zir'in is noomononmn omonrnnoniouonion i v As is well known one can prepare ether amino alcohols of the type I I Table II.

PART4 The products obtained by the herein described processes represent cogeneric mixtures which are the result of a condensation reaction or reactions. Since the resin molecule cannot be defined satisfactorily by formula, al-

. xylene.

. several hours.

though it maybe so illustrated in an idealized simplification, it is diflicult to actually depict the final product of; the 'icogen'eric mixture except in terms of the process itself. ,The condensation of the resin, the amine and formaldehyde is described in detail in applications Serial Nos.288,7 45 and 296,086, and reference is made to those applications fora discussion of the factors involved.

Little more need be said as to the actual procedure employed for the preparation of the herein described condensation products. The following example will serve by way of illustration:

Example 1b to an average of about 3 /2 phenolic nuclei, as the-value for n which excludes the 2 external nuclei, i. e., the resin was largely a mixture having 3 nuclei and 4 nuclei, excluding the 2 external nuclei, or 5 and 6 overall nuclei. The resin so obtained in a neutral state had a light amber color. Y

882 grams of the resin identified as 2a preceding, were powdered and mixed with a considerably lesser weight of xylene, to wit, 500 grams. The mixture was refluxed until solution was complete. It was then adjusted to approximately 33 to 38 C., and 296 grams of symmetrical di(hydroxyethyl)ethylenediamine were added. The mixture was stirred vigorously and formaldehyde used was a 30% solution and the amount employed was 200 grams. It was added in a little over 3 hours. The mixture was stirred vigorously and kept within a temperature range of 33 to 48 C. for about 17 hours. At the end of this time it was refluxed using a phase-separating trap and a small amount of aqueous distillate withdrawn from time to time. The presence of formaldehyde was noted. Any unreacted formaldehyde seemed to disappear within about 3 hours or thereabouts; As soon as the odor of formaldehyde was no longer particularly noticeable or detectible the phase-separating trap was set so as to elimiing this time any additional water, which was probably water of reaction which had formed, was eliminated by means of the trap. The residual xylene was permitted to stay in the cogeneric mixture. A small amount of the sample was heated on a water bath to remove the excess The residual material was dark red in color and had the consistency of a sticky fluid or tacky resin. The overall time for reaction was somewhat under 30 hours. In other examples it varied from 24 to more than 36 hours. The time can be reduced by cutting the low temperature period to approximately 3 to 6 hours.

Note that in Table II following there are a large number of added examples illustrating the same procedure. In each case the initial mixture was stirred and held ata fairly low temperature (30 to 40 C.) for a period of Then refluxing was employed until the odor of formaldehyde disappeared. After the odor of formaldehyde disappeared the phase-separating trap was employed to separate out all the Water, both the solution and condensation. After all the water had been separated enough xylene was taken out to have the final product reflux for several hours somewhere in the range of to C., or thereabouts. Usually the mixture yielded a clear solution by the time the bulk of the water, or all of the water, had been removed.

' Notethat 'as' pointed out previously, this procedure is illustrated by 24 examples in Table II. 1

TABLE I1 Strength 01 Reae- I Reac- Max. Ex. Resin Amt, Amine used and amount tormalrle- Solvent used tion tion distill No. used grs. hyde soln. and amt. temp;, time, temp.,

and amt- 0. hrs. C.

882 Amine A, 296 g 30% 200g... Xylene,;500 g 21-24 24 150 480 Amine A, 148 g 37% 81 g Xylene, 480 g 20-23 27 156 633 do i do Xylene, 610 gm. 22-27 25 142 441 Amine B, 176 g 30% 100 g--- Xylene, 300 g 20-25 28 145 480 do .s 37% 81 g Xylene, 425 g 23-27 34 150 033 tl 30% 100 g Xylene, 500 g 25-27 30 1'52 882 Amine C, 324 g 37% 162 g- Xylene, 625 g 23-26 38 141': 480 Amine C, 162 g 30% 100 g Xylene, 315 g -21 143 633 do 'd Xylene, 535 g 23-24 25 140 473 Amine 13,256 g Xylene, 425 g 22-25 25 148 511 d0 Xylene, 450 g. 20-21 25 I 158 665 0 Xylene, 525g 21-25 28* 152 441 Amine E, 208 g Xylene, 400 gm. 22-24 26 143v 480 do do 25-27 36 144 595 .....do Xylene, 500 g' 26-27 34 1'41' 441 Amine F, 236 g Xylene, 400 g n 21-23 25, 153. 1 480 do l0 20-22 28 150 511 Amine F,.236.g' Xylene, 500 g 23-25 27 155 409 Amine G, 172 g Xylene, 400 g 20-21 34 150 542 .do. Xylene, 450 g 20-24 36 152 547 Amine H, 221 g- Xylene, 500 g 20-22 30 148 441 do Xylene, 400 g 20-20 24 143 595 Amine I, 172 g. do. Xylene, 450 m... 20-22 32 151 391 Amine I, 86 g 30% 50 g Xylene, 300 gm. 20-26 36 147 As to the formulas of the above amines 'referredvto' as Amine A through Amine I; inclusive; see immediately following:

Amine G- no GHiCHqNHCH:C1IOHCHrNHCHgCIhOH Amine nno cmcnmrmon,

H0 CHiCH2NH- H2 Amine I- CHsNHCHz casement-onion CHsNHCHg PART 5 In preparing oxyalkylated. derivatives of products. of the kind which appear as'exarnples in Part 3, I have found it particularly advantageous to use laboratory equipment which permits continuous oxypropylation and oxyethyla" tibn'. More specific reference will be made to treatment with glycide subsequently in the text. The oxyethylation step is, of course, the same as the oxypropylation step' insofar that two low boiling liquids are handled in eachv instance; What immediately follows refers'to oxyethylation and it is understood that oxypropylation can he,

handled conveniently in cxactly the same manner. Thai oxyalkylation of the amine resin condensates is carried out byprocedures which are commonly used for'the oxyalkylation of oxyalkylation susceptible materials. The factors tobeconsidered are discussed in some detail in applications Serial Nos. 301,806 and 310,554 and refer;

ence is made to those applications for a description of suitable equipment, precautions to be taken and a general discussion of operating technique. The following examples are given by way of illustration.

Example- 10 The oxyalkylation-susceptible compound employed isthe one previously described anddesignated as Example 1b. Condensate 1b was in turn obtained from sym-- metrical di(hydroxycthyl)cthylene diamine, previously described for convenience as Amine A, and the resin previously identified as Example 211. Reference 'toTable I shows that this particular resin is obtained from paratertiarybutylphenol and formaldehyde. 12.02 pounds of this resin condensate were dissolved in 5 pounds of solvent (xylene) along with one pound of finely powdered caustic soda as a catalyst. Adjustment was made in the autoclave to operate at a temperature of approximately C. to C., and at a pressure of about 15 to 20 pounds. In some subsequent examples pressures up to 35 pounds were employed.

The-time regulator was set so as to'inject the ethylene I oxide in approximately 1% hours, and then continue stirring for 15 minutes longer. The reaction went readily and, as a matter of fact, the oxide was taken up almost immediately. Indeed the reaction was complete in less than an hour. The speed of reaction, particularly at the low pressure, undoubtedly was due in a large measure to excellent agitation and also to the. comparatively high concentration of catalyst. The amount of ethylene oxide,

introduced was equalin weight to the initial condensation product, to wit, 12.02 pounds. This represented amolal ratio of 27.3 moles of ethylene oxide per mole of contion as far as solubility or emulsifying power was con cerned and also for the purpose of making some tests on various oil field emulsions. The amount withdrawn was so small that no cognizance of this fact is included in this data, or subsequent data, or in .the data presented in tabular form in subsequent Tables 3 and 4.

The size of the autoclave employed was 25 gallons. In innumerable comparable oxyalkylations I have withdrawn a substantial portion at the end of each step and continued oxyalkylation on a partial residual sample. This was not the case in this particular series. Certain examples were duplicated as hereinafter noted and subjected to oxyalkylation with a different oxide.

Example 20 This example simply illustrates the further oxyalkylation of Example 1c, preceding. .As previously stated, the oxyalkylation-susceptible compound, to wit, Example 1b, present at the beginning of the stage was obviously the same as at the end of the prior stage (Example about 12.02 pounds. The amount of oxide present in the initial step was 12.02 pounds, the amount of catalyst remained the same, towit, one pound, and the amount of solvent remainedthe' same. The amount of oxide added was another 12.02 pounds, all addition of oxid'e' inthese various stages being based on the addition of this particular amount. Thus, at the'end of the oxyethyla -f tion step the amount of oxide added was a total of 24.04

p'oundsand the molal ratioof ethylene oxide to resin? condensate was 54.7 to 1.

The theoretical molecular weight was'3606.

The maximum temperature during the "operation was 130. C. Ito 135 C."The maximum pressure was in the rangeof to. pounds. The time period was a ittle less than" before, to wit, only minutes.

Eicrzmple dc I The oxyalkylation proceeded in the same manner described in Examples lc and 2 c.;There was no added solvent and no added catalyst. The oxide added was 12.02. pounds and the'total oxide at the end of the oxy- The molalqratio of ethylatio'n step was-.3606 pounds.

oxide to condensate'was 82.0 to 1. Conditions as far as temperature,=p'ressure and time were concerned were all thefsame as in Examples 10 and 2c. The time period was one'hour.

Example 40 same as inprevious examples. The time period was slightly longer, to .wit, 2% hours. The theoretical mo-- lecul'ar weight'at'the end of the prior stepwas 4808, and at 'the'end 'ofthi's' step 6010. The reaction showed some slowing at 'thi's'particular stage.

' Example vent was introduced. but .3 pound caustic soda was added. Thethe'oretica'l molecular weight at the end of the agitationperiod was 7212,"and the molal ratio of oxide to 'f '70 The 'oxyethylation continued with the introduction of another"l2.02 pounds of ethylene oxide. No moresolresin condensate was 136.5 to 1. The time period, however, was slightly less than before, to wit, 2 hours. Operating temperature and pressure remained the same as in the previous example.

Example The same procedure was followed as in the previous examples. The amount of oxide added was another 12.02 pounds, bringing the total oxide introduced to 72.12 pounds. The temperature and pressure during this period were the same as before. There was no added solvent. The time period was 3 hours.

Example 76 The same procedure was followed as in the previous six examples without the addition of more caustic or more solvent. The total amount of oxide introduced at the end of the period was 84.14 pounds." The theoretical molecular weight at the end of the oxyalkylation period was 9616. The time required for the oxyethylation was the same as in the previous step, to wit, 3 hours.

Example 80 This was the final oxyethylation in this particular series. There. was no added solvent and no added catalyst. The total amount of oxide added at the end of this step was 96.16 pounds. The theoretical molecular weight was 10,818. The molal ratio of oxide to resin condensate was 218 to one. Conditions as far as temperature and pressure were concerned were the same as in the previous examples and the time required for oxyethylation was slightly longer than in the previous step, to wit, 4 hours.

The same procedure as described in the previous examples was employed in connection with a number of the other condensates described previously. All these data have been presented in tabular form in a series of four tables, Tables III and IV, V and VI.

In subsequently every case a 25-gallon autoclave was employed, although in some instances the initial oxyethylation was started in a 15-gallon autoclave and then transferred to a 25-gal1on autoclave. This is immaterial but happened to be a matter of convenience only. The solvent used in all cases was xylene. The catalyst used was finely powdered caustic soda.

Referring now to Tables III and IV, it will be noted that compounds 10 through 400 were obtained by the use of ethylene oxide, whereas 41c through 80c were obtained by the use of propylene oxide alone.

Thus, in reference to Table III it is to be noted as follows.

The example number of each compound is indicated in the first column. I

The identity of the oxyalkylation-susceptible compound, to wit, the resin condensate, is indicated in the second column.

The amount of condensate is shown in the third column.

Assuming that ethylene oxide alone is employed, as

happens to be the case in Examples 1c through 400, the

1 7 The 9th column shows the theoretical molecular weight at the end of the oxyalkylation period.

The 10th column states the amount of condensate present in the reaction. massv at the end of the period;

As pointed out previously, in this particular series the amount of reaction mass withdrawn for examination was so small that it was ignored and for this reason the resin condensate in columnlO coincides with the figure.

Column 16 can be ignored for the reason that no.

propylene oxide was employed. I

Referring now to Table VI. It is to be noted that the first column refers to Examples 10, 20, 3c, etc.

The second column gives the maximum temperature employed during the oxyalkylation step and the third.

column gives the maximum pressure.

The fourth column gives the time period employed. The last three columns show solubility tests by shaking a small amount of the compound, including the solvent present, with several volumes of water, xylene and kerosene. It sometimes happens that although xylene is com-v paratively small amounts will dissolve in the concentrated material, when the concentrated material in turn is. di-

luted with xylene separation takes place.

Referring to Table IV, Examples 410 through 800 are 30 of caustic soda, and 5.0 Pounds of the solvent.

18 the counterparts of Examples 1c through 40c, except that the oxide employed is propylene oxide instead of ethylene oxide. Therefore as explained previously, four columns are blank, to wit, columns 4; 8, Hand 15.

Reference is now made to'Table V. It is to be noted these compounds are designated by d numbers, 1 1-, 2d, 3d, etc}, through and including 32d. They. are derived, inturn, from compounds in the c se'ries,for example, 37c, 40c, 46c, and 77c. These compounds involve the use of both ethylene oxide and propylene oxide. Since compounds 10 through. 40c were obtained by the use of ethylene oxide, it is obvious that those obtained-from 37c and 40s, involve the use of ethylene oxide first, and pro? pylene oxide afterward. Inversely, those compounds obtained from 46ckand 77c obviously come from a prior seriesin which propylene oxide wasus ed first.

Inthe preparation of this series indicated by the small letter, d, as 1d, 2d, 3d, etc., the initial 0 series suchas 370, 40c, 46c, and 77c were duplicated and the oxyaI- kylation stopped at the point designated instead of being carried further asmay have been the case in the original. oxyalkylation step. Then oxyalkylation proceeded by using the second oxide as indicated by the previous ex planation, to wit, propylene oxide'in, 1d through 16d,

and, ethylene oxide in l7d-through 32d, inclusive.

In examining the table beginning with 1d, it will benoted, that the initial product, i. e., 370, consisting of the reaction product involving 12.02 pounds of the resin condensate, 30.05- pounds, of ethylene oxide, 1.0 pounds It is to be noted that reference to the catalyst in Table V refers to the total amount of catalyst, i. e., the catalyst present from the first oxyalkylation step plus added catalyst, if any. The same is true in regard to the solvent."

TABLE III Composition before Composition'at end Molal ratio Molec Ex. No. wt. 0-8 0-8 Ethl. Propl. Gata- Sol- O-S' Ethl. Propl. Cata- Sol. Ethyl. Propl; based. cmpd., cmpd., oxide, oxide, lyst, vent, cmpd., oxide, oxide Iyst, vent, oxide oxide on theex.No. lbs. lbs. lbs. lbs. lbs. lbs. lbs. lbs. lbs. lbs. to oxy to ox oretlcal alkyl.- alky value suscept. suscept.

cmp cmpd.

Herr ra-z-tz-zrrirr s rrrer'r-FHr-Hr 'r- H WWWWOOOOWNWWOOOOKIKIQMMNMNOJQJWWOOOONwWWOOOO Oxyallrylation-suseeptible Molec. wt. based value 804 89 20 28 2 2542 5236227..06 .2 434. mmwmummwwmmmammmnmmmmmwmmwuwumwmwwm 2 2w4-6 &0 3 4 2 4 :w6 9 2 4-6 2 45 6 0w25623457 Molec. wt. based theoretical I value Prop].

oxide on theelkyl.

empd.

Prop].

oxide on Molal ratio to oxy-- to oxyoretlcal oxide alkyl. susoept. susoept.

empd

0 11223 01223334555 5 .m5 5 LLLLLL11 11 11111111111 Molal ratio 1:. suscept. d. empd.

Ethyl. oxide alkyl suscep cmp Sol. Ethyl. vent, lbs.

S01. vent, lbs.

2222255511111555222226661111155511011555 LLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLL Composition at end Pro 1. OX! lbs.

00000000333883882225555511115555 llllllLLLLLLLLLLLLLLLLLLLLLLLLLL Composition at end Prop]. oxide,

lbs.

Ethl. oxide,

is... Oxide, lbs.

OEJSd l bs. I,

RUE-35555588888888 00000000000000 0000000000000000 TABLE IV Solvent, lbs.

TABLE V Sol- 7 vent, lbs.

22222555111115552 22226661111155511111555 LLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLL 2 222222222222 2 2222222 22 0 000000000000 0 OOOOOOOMOOWM assasaassasaasao Catalyst, lbs.

Pro 1.

lbs.

LLLLLLLLLLLLLLLLLLLLLLLL LLLLLLL .Pro 1.

lbs.

Ethll. oxide, oxi

lbs.

v 55 5 0000000 mOOODOOOHMMMMMMMOOMOM Ethl. oxide, oxi

lbs.

Composition before lbs.

Composition before fo-s' lbs.

o-s cmpd., ompd., ex. No.

Oxyalkylation-susceptible ELVNOL I 'Oxvalkylation-suseeptible.

i. e., that from the first oxyalkylation step plus added solvent, if any.

In this series, it will be noted that the theoretical molec- 22 use ethylene oxide,.and then'go. back to propylene oxide; or, one could use a combination in which butylene oxide is used along with either one of thetwo oxides just mentioned, or a combination of both of them.

ular weights are given prior to the oxyalkylation step 5 The colors of the products usually vary from a reddish and after the oxyalkylation step, although the value at amber tint to a definitely red, and amber. The reason the end of one step is the value at the beginning of the is primarily that no eifort is made to obtain colorless next step, except obviously at the very start the value resins initially and the resins themselves may be yellow, depends on the theoretical molecular weight at the end amber, or even dark amber. Condensation of a nitrogof the initial oxyalkylation step; i. e., oxyethylation for enous product invariably yields a darker product than 1:! through 16d, and oxypropylation for 17d through 32a. the original resin and usually has a reddish color. The

It will be noted also that under the molal ratio. the solvent employed, if Xylene, adds nothing to the color but values of both oxides to the resin condensate are in one may use a darker colored aromatic petroleum solvent. cluded. Oxyalkylation generally tends to yield lighter colored The data given in regard to the operating conditions is products and the more oxide employed the lighter the substantially the same as before and appears in Table VI. color of the product. Products can be prepared in which The products resulting from these procedures may conthe final color is a lighter amber with a reddish tint. tain modest amounts, or have small amounts, of the sol- Such products can be decolorized by the use of clays, vents as indicated by the figures in the tables. If desired bleaching chars, etc. As far .as use in demulsification is the solvent may be removed by distillation, and particu- 20 concerned, or some other industrial uses, there is no justi-- larly vacuum distillation. Such distillation also may refication for the cost of bleaching the product. move traces or small amounts of uncombined oxide, if Generally speaking, the amount of alkaline catalys present and volatile under the conditions employed. present is comparatively small and it need not be removed.

Obviously, in the use of ethylene oxide and propylene Since the products per se are alkaline due to the presence oxide in combination one need not first use one oxide and of .a basic nitrogen, the removal of the alkaline catalyst then the other, but one can mix the two oxides and thus is somewhat more difficult than ordinarily is the case for obtain what may be termed an indifferent oxyalkylation, the reason that if one adds hydrochloric acid, for example, i. e., no attempt to selectively add one and then the other, to neutralize the alkalinity one may partially neutralize or any other variant. the basic nitrogen radical also. The preferred procedure Needless to say, one could start with ethylene oxide and is to ignore the presence of the alkali unless it is objecthen use propylene oxide, and then go back to ethylene tionable or else add a stoichiometric amount of concenoxide; or, inversely, start with propylene oxide, then trated hydrochloric acid equal to the caustic soda present.

TABLE VI Max. Max Solubility Ex. temn, pres Time, No. O. p. s. i. hrs.

Water Xylene Kerosene Insoluble TABLE VI'(continued).

Max. Solubility pres,

Time, p. s. 1. his.

Kerosene Soluble.

Do. Dlsperslble. Soluble.

Do. Insoluble.

Do. Dispersible.

Do. Soluble. Insoluble.

0. Dlsperslble. Do. Soluble.

7 Do. .Dlspersible.

Insoluble. Do.

PART 6 The conversion of the oxyalkylated basic condensate of the kind previously described into the corresponding salt of gluconic acid is a simple operation since it is'noth- 7 ing more nor less than neutralization. The condensate invariably contains two basic nitrogen atoms. One can neutralize either one or both nitrogen atoms.

Another factor which requires some consideration would be the presence of basic catalysts which were used during the oxyalkylati on process. Actual tests indicate that the basicity appears to be somewhat less than would be expected, particularly in examples in which oxyalkylation is comparatively high. The usual procedure has been to add enough gluconic acid to convert the product into the salt as predetermined and then note whether or not the product showed any marked alkalinity. If so, slightly more gluconic acid was added until the prodnot was either just barely acid or just very moderately alkaline. For sake of clarity this added amount of gluconic acid, if required, is ignored in subsequent Table VIII.

Gluconic acid is available as a 50% solution.

salts, or at least, the salts of the herein described oxyalkylated condensates. Such salts appear to be stable, or

a temperature as high as 150 C. orthereabouts.

Asjhas been pointedj out previously the presentjappli Dehydration causes decomposition. This is not true of the cation is a cont-inuationin-part of certain co-pending applications and reference is made to aiorementioned copending application, Serial No. 329,485, filed January 2, 1953. The co-pending application, Serial No. 329,485,

i filed January 2, 1953, described the neutralization of the nonoxyalkylated condensate.

Reference now is made .to Table VII which, in essence, is substantially the same as much of the data in Table II but includes additional calculations showing the larnountof gluconic acid (50%) required to neutralize a certain amount of condensate; for instance, compare Example, 12 in Table VII with Example 1b in Table II. In any event, since there were available various oxyalkylated derivatives of condensates 1b and 10b, these par- ,ticular oxy-alkylated derivatives were used for the purpose ot-fillustrating salt formation, all of which is illustrated in Table VIII.

Briefly stated, referring to Example 1e in Table VII 5 it to be-noted that 1202 grams of the nonoxyalkylated condensate required 1570 grams of 50% gluconic acid for neutralization. Reference to Table VI-II shows that 1202 :grams of ilthe condensate Example 1b, when converted into the oxyalkylated derivative as obtained from 2c,

were equivalent to 4135 grams. Therefore, 4135 grams were selected as the appropriate amount of oxyalkylated material tor neutralization simply for .the reason that calculationjwas eliminated.

Thef-oxyalkylated condensate generally is a liquid and,

75 3 as arulefl contains a comparatively small amount of solvent. Note the examples in Table VIII. The solvent happened to be xylene in this instance but could have been benzene, aromatic petroleum solvent, or the like. Needless to say, the solvent could have been removed from the oxyalkylated derivative by use of vacuum distillation and this is particularly .true if benzene happened to be the solvent. ation invariably is lighter than the initial material for the reason that the condensate is dark colored and oxyalkylation simply dilutes the color. In other words, the product may be almost white, pale straw color, or an amber shade with a reddish tint. I

The product either before or after neutralization can be bleached with filtering clays, charcoals, etc. The procedure generally is, as a matter of convenience, to form the salt and then dilute with a solvent if desired, using such solvent as xylene or a mixture of two-thirds xylene and one-third ethyl alcohol or isopropyl alcohol, to give approximately a 50% solution. If there happened to be any precipitate the solution is filtered. If desired, the product prior to dilution could be rendered anhydrous simply by adding benzene and subjecting the mixture to reflux action under a condensate or a phaseseparating trap. If there happened to be any tendency for the product to separate them the solvents having hydrotropic properties, such as the diethylether or ethyleneglycol, or-the like, are used.

The salt formation is merely a matter of agitation at room temperature, or at a somewhat higher temperature if desired, particularly in a reflux condenser. Usually agitation is continued for an hour but actually neutralization may be a matter of minutes. In some instances after salt formation is complete and the product is diluted to approximately 50%, I have permitted the solution to stand for about 6 to 72 hours. Sometimes, depending on composition, there is a separation of an aqueous phase or a small amount of salt-like material. On a laboratory scale the procedure is conducted in .a separatory funnel. If there is separation of an aqueous phase, or .any other undesirable material, at the bottom of the separatory funnel it is merely discarded. The salt form, of course, can be bleached in the same manner as previously described for the oxy-alkylated derivative. Usually the color of the salt is practically the same as the oxyalkylated derivative. For various commercial purposes in which the product is used there is no justification for the added cost of decolorization. The'salt form can be dehydrated or rendered solvent-tree by the usual procedure, i. e., vacuum distillation, after the use of a phase-separating trap.

The product as prepared, without attempting to decolorize, eliminate any residual catalyst in the form of a The product obtained from oxyalkylsalt, and without any particular efiort to obtain absolute neutrality or the equivalent, is more satisfactory for a number of purposes where the material is useful, such as a demuls'ifier forpe-troleum emulsions of the water-inoil type, or oil-in-water type; for the prevention of corrosion of metallic surfaces, especially ferrous'surfaces; or as an asphalt additive for anti-stripping purposes.

The condensates priorto oxyalkylation may be solids but are generally viscousliquids or liquids which are almost solid or tacky. Oxyalkylation reduces such ma terials to viscous liquids or thin liquids comparable to polyglycols, of course depending primarily on the amount of alkylene oxide added. After neutralization the physical characteristics of the products are about the same and in Needless to say, if?

the majority of cases-are liquids. a solvent were added, even if the material were solid initially, it would be converted into a liquid form. a

In light of what has been said and the simplicity of. salt formation it does not appear that any illustration is required. However, previous reference has been made to Table VIII. The first example in Table VIII is Example If. The following is more specific data in regard to Example 11.

Example If of 30% formaldehyde. All this has been described previously. The weight of the condensate on .a solvent-free basis was 1202 grams. This represented approxmately 56 grams of basic. nitrogen. Referring to, Table VIII it will be noted that 12.02 pounds of the condensate werev combined with 24.04 pounds .of ethylene oxide and .5, pounds of solvent. oxyalkylated derivative 20 were placed in a laboratory device which, although made of'metal, was the equivalent.

of a separatory funnel. To this there were added 570 grams of gluconic acid and the mixture stirred vigorously for an hour and allowed to stand at room temperature, or thcreabouts, for about 1 /2 days.

In such instances where a small amount of dre gs appeared at the bottom a slight amount of material was.

drawn off and the remainder diluted with xylene to bring it to approximately 50%.

A number of other examples are included in Table VIII. For convenience, Tablev VII is included atthis point just preceding Table ,VIIL.

TABLE VII Salt formation calculated on Condensate in turn derived frombasis of non-oxyalkylated Salt condensate from Salt, con- I Ex. den- 37% Wt. of No. sate Resin Amt. Amt. AmlIlB form- -T den- Theo. 50% glll" N0. N0. resin, Solvent sol- Amine used used aldesate on basic conic gins. vent, gins hyde, solventnitrogen, acid, gms. grns. free basis, gms. gms.

sms- 9 882 Xylene 500 296 2 200 1, 202 56' 1,570 480 do 480 148 81 640 28 785 633 do 610 148 81 793 .28. 785: 441 do 300 176 2 100 629 28 785 480....(10 425 176 I 81 S68 28 785 633 d 600 176 2 100 851 28 785 882 d 625 324 162 1,230 56 1,570 480 do 315 162 9 100 654 28 785 633 do 535 162 '100 807 28 785 473 .do 425 256 z 100 741v 28 785 511 do. 450 256 2 100 779 28 785 525 256 2 100 933 28 785 500 296 3 200 1, 202 28 392 300 176 I4 100 629 28 392 625 324, 162 1, 230 28 392 1 For description of amines see notes following Table II.

I formaldehyde.

882 grams of the resin were dissolved In any event, 4135 grams of the;

TABLE V111 Grams of oxyallrylated compound v Obtained in turn from Percent I which is equiv. 50 percent i Oxya1kylcondento grams of conglueonic Ex. No. ated destate in dens-ate acid to rlvative, oxyalkylneutralex. No. 'ated de- 1 ize, grams Conden- Amt. con- EtO PrO Solvent rlvative Oxyalkyl- Condensate, densate, amt;., amt., amt., ated comsate ex. No. lbs. lbs. lbs. lbs. pound PART 7 diluents. Miscellaneous solvents such as pine oil, carbon tetrachloride, sulfur dioxide extract obtained in the refining of petroleum, etc., may be employed as diluents.

Similarly, the material or materials employed as the demulsifying agent of my process may be admixed with one or. more of the solvents customarily used in connection with conventional demulsifying agents. Moreover, said material or materials maybe used alone or in admixture with other suitable well-known classes ofdemulsifying agents; It is well known that conventional demulsifying agents may 'be used'in a water-soluble form, or in an oil-soluble form, or in a form exhibiting both oiland water-solubility. Sometimes they may be used in a form which exhibits relatively limited oil-solubility. However, since such reagents are frequently used in a ratio of .1 to 10,000 or 1 to 20,000, or 1 to 30,000, oreven 1 to 40,000, or 1 to 50,000 as in desalting practice, such an apparent insolubility in oil and water is not significant because such reagents undoubtedly have'solubility within such concentrations. This same fact is true in regard to the material or materials employed as thedemulsifying agent of my process.

In practicing the present process, the treating or demul 3 to the art, described, for example, in Patent 2,626,929, dated January 27, 1953, Part 3, and reference is made thereto for a description of conventional procedures of demulsifying, including batch, continuous, and down-thehole demulsification, the process essentially involving introducing a small amount of demulsifier into a large amount of emulsion with adequate admixture with or without the application of heat, and allowing the mixture to stratify.

sifying agent is used in the conventional way, well known An ammonium salt of a polypropylated naphthalene monosulfonic acid, 24%;

A sodium salt of oil-soluble mahogany petroleum Qsnlfonic acid, 12%; Y

A high-boiling aromatic petroleum solvent, 15%; Isopropyl alcohol, 5%. i The above proportions areall weight percents.

Having thus described my invention, what I claim as new and desire to secure by Letters Patent is:

1. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including the gluconic acid salts of the basic oxyalkylated products obtained in turn inI-the process'of condensing (a) an oxyalkylation-sus ceptible, fusible, non-oxygenated organic solvent-soluble,

water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding'to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-fonmiing reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde ha'ving not over 8 carbon atoms and reactive toward said phenol; said resin being formed inthe substantial absenceof trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substi- (tuted in the 2,4,6 position; (b) a basic hydroxylated polyamine havingat least one secondary amino group and 1 pyrolytic point of the reactants and resultants of reac-- tion; and with the proviso that the'resinou's condensation product resulting from the process be heat-stable and oxy- At noted above, the products herein described'may be 7 used not only in diluted form, but also may be used admixed with some other chemical demulsifier. A mixture -A cyclohexylamine salt of a polypropylated naphthalene monosulfonic acid, 24%;

alkylation-susceptible; followed by an oxyalkylation step by means of an alpha beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene 'oxide, glycide and methylglycide.

2. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including the gluconic acid 29 salts ofthe basic oxyalkylated products obtainedin turn in' the process of condensing (a) an oxyalkyl'ation-su's cepti-ble, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the rformula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) abasic hydroxylated polyamine having at least one secondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and With the further proviso that the polyamine be free 'from any primary amino radical, any substituted imidazoline radical, and any substituted tetrahydropyrimidine radical; and formaldehyde; said condensation reaction being conducted at a temperature sufiiciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; with the added proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule; and with the further proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by an oxyalkylation step by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consist: ing of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide.

3. A process for breaking petroleum emulsions of the water-in-oiltype characterized by subjecting the emulsion to the action of a demulsifier including the gluconic acid salts of the basic oxyalkylated products obtained inturn in the process of condensing (a) an oxyalkylation-susceptible, fusible non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a. difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula that the polyamine be free from any primary'amino radical, any substituted imidazoline radical, and any substituted tetrahydropyrimidine radical; and (0) formaldehyde; said condensation reaction being conducted at a tempera ture *sufiiciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction, with the-proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which eachof theth re reactantsghavejc tri'butcd part of the ultimate molecule by virtue bf a formaldehyde-derived methylene bridge connecting the amino nitrogen atom with a resin molecule; and with the "further proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by an oxyalkylation step by means of an alphabeta alkylene oxide having, not more than 4 carbon atoms and selected from the class'consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide.,

4. A process for brcakingpetroleum emulsions of the water-in-oil type characterized by subjecting the emula sion to the action of a demulsifier including the vgluconic acid salts of the basic oxyalkylated products obtainedjin the formula I v in which R is an aliphatic hydrocarbon radical having: at least 4 and not more than 24 carbon atoms and sub-- stituted in the 2, 4, 6 position; (b) a basic hydroxylated polyamine having atleast one secondary amino group and;

having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amino. radical, any substituted imidazoline radical, and any sub-- stituted tetrahydropyrimidine radical; and (c) formalde hyde; said condensationreaction being conducted at a.

temperature sufliciently high to eliminate water and below the pyrolytic pointof the reactants and resultants of reaction; with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the threereactants have. contributed part of the ultimate molecule by virtue of an formaldehyde-derived methylene bridge connecting the' amino nitrogen atom of reaction with a resin molecule; with the further proviso that the molar ratio of reactants be approximately 1, 2 and 2 respectively; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylationsusceptible; followed by an oxyalkylation step by means of an alpha-beta alkylene oxide having not more than" 4 carbon atoms and selected from the class consisting of" ethylene oxide, propylene oxide, butylene oxide, glycide v and methylglycide. v

5. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion,

to the action of a demulsifier including the gluconic acid salts of the basic oxyalkylated products obtained in turn in the process of condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble,

water-insoluble, low-stage phenol-aldehyde resin havingan average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei resin molecule; said'f resin being difunctional only in regard to methylol 'j" forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and analdehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed-in the substantial" r 31 absence of trifunctional phenols; 'said phenol being of hai ml l 'OHt in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2, 4, 6 position; (b) a basic hydroxylated 'polyamine having at least onese'condary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogenatom, and with the further proviso that the polyamine be freefrom any primary amino radical, any-substituted--imidazoline radical, and any substituted 'tetrahydropyrimidine radical;- and formaldehyde; said condensation reaction beingconductedat a temperaturesufliciently high to eliminate water and-below the pyrolytic' point of the reactants and resultants'of reaction; with the proviso that the condensationreaction be conducted so as" to produce a significant portion'of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge,

connecting the amino nitrogen'atom ofreaction with a resin molecule; with the further proviso that said procedure involves the use of a solvent, with the further proviso that the molar ratio of reactants be approximately 1, 2 and 2 respectively; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by an oxyalkylation step by means of an alphabeta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide. 1

6. A- process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action ofademulsifier including the gluconic acid salts of the basic oxyalkylated products obtained in turn in the process of condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-formaldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin'being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being'formed in the substantial absence of trifunctional phenols; said phenol being of the formula r in which' R is an aliphatic hydrocarbon radical having at least 4, and not more than 24 carbon atoms and substituted in the 2, 4, 6 position; (b)"a basic hydroxylated' polyamin'e having at least one secondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amino radical, any substituted imidazoline radical, and

any substituted tetrahydropyrimidine radical; and (0) 32 resin molecule; with the added proviso that thepmolar ratio of reactants be approximately 1, 2 and 2,- respec-? tively; with the further proviso that said procedure; involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by an oxyalkylation step by meansof an alphabeta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide. 3 v 7. A process for breaking petroleum. emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including the gluconic acid salts of the basic oxyalkylated products obtained in turn in the process ofcondensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-formaldehyde resin, having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin mole cule; said resin being difunctional only in regard'to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of trifunctional phenols; said phenol beingofthe formula in which Ris an aliphatic hydrocarbon radical having" at least 4 and not more than 14 carbon atoms and'substituted in the 2,4,6 position; (b) a basic hydroxylated polyamine having at least one secondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be'free from any primary amino radical, any substituted imidazoline radical, and

any substituted tetrahydropyrimidine radical; and (0)" formaldehyde; said condensation reaction, being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction, with the proviso that'the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate mole-V cule by virtue of a' formaldehyde-derived. methylene bridge connecting the amino nitrogen atomof reaction:

with a resin molecule; with the added proviso that the molar ratio of reactants be approximately 1, 2 and 2 respectively; with the further proviso that said procedure 8. A process for breaking petroleum emulsions of the water-in-oil typecharac'terized by subjecting the emulsion to the actionof a demulsifier including the gluconic acid salts of the basic oxyalkylated products obtained in turn in the process ofcondensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, 'Water-insoluble, low-stage phenol-formaldehyde resin having an average molecular weight "corresponding to at least 3 and not over 6 phenolic nucleiper resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being, derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial in which R is an aliphatic hydrocarbon radical having at least'4 and not more than 14 carbon atoms and sub stituted in the 2,4,6 position; (b) a basic hydroxylated polyamine having at least one secondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amino radical, any substitutde imidazoline radical, and any substituted tetrahydropyrimidine radical; and ('c) formaldehyde; said condensation reaction being conducted at a temperature above the boiling point of water and below 150 C., with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino'nitrogen atom of reaction with a resin molecule; with the added proviso that the molar ratio of reactants be approximately 1, 2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by an oxyalkylation step by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide.

9. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including the gluconic acid salts of the basic oxyalkylated products obtained in turn in the process of condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-formaldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is a para-substituted aliphatic hydrocarbon radical having at least 4 and not more than 14 carbon atoms; (12) a basic hydroxylated polyamine having at least one secondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amino radical, any substituted imidazoline radical, and any substituted tetrahydropyrimidine radical; and (c) formaldehyde; said condensation reaction being conducted at a temperature above the boiling point of water and below 150 C., with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehydederived methylene bridge connecting the amino nitrogen atom of reaction with a resin molecule; with the added proviso that the molar ratio of reactants be approximately 1, 2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation productresuln ing from the process be heat-stable and oxyalkylation-v susceptible; followed by an oxyalkylation step. by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide;1 glycide and methylglycide.

10. The process of breaking petroleum emulsions as defined in claim 1 wherein the oxyalkylation step of the manufacturing process is limited to the use of both ethylene oxide and propylene oxide in combination.

11. The process of breaking petroleum emulsions as;

defined in claim 2 wherein the oxyalkylation step of the manufacturing processis limited to the use of both ethylene oxide and propylene oxide in combination.

12. The process of breaking petroleum emulsions as defined in claim 3 wherein the oxyalkylation step of the manufacturing process is limited to the use of both ethylene oxide and propylene oxide in combination.

13. The process of breaking petroleum emulsions as defined in claim 4 wherein the oxyalkylation step of the manufacturing process is limited to the use of both ethylene oxide and propylene oxide in combination.

14. The process of breaking petroleum emulsions as v defined inclaim -7 wherein the oxyalkylation step. of the manufacturing process is limited to the use of both ethyl-.1

ene oxide and propylene oxide in combination.

17. The process of breaking petroleum emulsions'gas defined in claim 8 wherein the oxyalkylation step offlthe manufacturing processis limited to the use of both ethyl-.

ene oxide and propylene .oxide in combination.

18. The process of breaking petroleum emulsions as:

defined in claim 9 whereintheoxyalkylation step ofthe manufacturing process is limited -to the use of bothethylene oxide and propylene oxide in combination.

19. The process of claim l with the provisothat the hydrophile properties of the gluconic acid salt ofthe oxyalkylated condensation product in an equal Weight of.

xylene are sufficient to produce an emulsion when said xylene solution is shaken vigorously with one to three' volumes of water.

'20. The process of claim 2 with the proviso that the hydrophile properties of the gluconic acid salt of theoxy- V alkylated condensation product in an equal weight of xylene are sufiicient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water. 21. The process of claim 3 with the proviso that the hydrophile properties of the gluconic acid salt of the oxyalkylated condensation product in an equal weight of xylene are sufiicient to produce an emulsion when said xylene solution is shaken vigorously with one to three' volumes of water.

22. The process of claim 4 with the proviso that the hydrophile properties of the gluconic acid salt of the oxyalkylated condensation product in an equal weight of xylene are sufficient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water. p

23. The process of claim 5 with the proviso that, the hydrophile properties of the gluconic acid salt of the oxyalkylated condensation product in an equal weight of xylene are sufiicient to produce an emulsion when said I xylene solution is shaken vigorously with one to three volumes of water.

24. The process of claim 6 with the proviso that the hydrophile properties of the gluconic acid salt of the oxy-' alkylated condensation product in art-equal weight of xylene are sufficient to produce an emulsion when said xylene solution is shaken .vigorously with one t-o'three volumes of water. t I a 'I 25. The process of claim 7 with" theproviso that the hydrophile properties of the gluconic acid salt of the'oxyalkylated condensation product in anequal weight of xylene are suflicient toproduce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water.

26. The process of claim 8 with the proviso that the hydrophile properties ofthe gluconic acid salt of the oxyalkylated condensation product in an equal weightof xylene are sufficient to produce an emulsion when said Xylene solution is shaken vigorously with one to three volumes of water.

27. The process of claim 9 with the proviso that the hydrophile properties of the gluconic acid salt of the. oxyalkylated condensation product in an equal weight of xylene are sufficient to produce an emulsion when said 7 xylene solution is shaken vigorously with one to three volumes of water.

28. The process of claim 10 with the proviso that the hydrophile properties of the gluconic acid salt of the oxyalkylated condensation product in an equal weight of xylene are suflicient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water.

'29. The process of claim 11 with the proviso that the hydrophile properties of the gluconic acid salt of the oxyalkylated condensation product in an equal weight of xylene are suflicient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water.

'30., The process of claim 12 with the proviso that the hydrophile properties of the gluconic acid salt of the oxyalkylated condensationproduct in an equal weight of xylene are suflicient to produce an emulsion when said xylene solution is shaken vigorously with one tothree volumes of water. a Y

31. The process of claim 13 with the proviso that the hydroph-ile properties of the glucon ic acid salt of the oxyalkylated condensation product in an equal weight of xylene are s-ufiicient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water. 7

32. The process of claim 14 with the proviso that the hydrophile properties of the gluconic acid salt of the oxyalkylated condensation product in an equal weight of xylene are suflicient to produce an, emulsion when said xylene solution is shaken vigorously with one to three volumes of water.

33. The process of claim 15 with the proviso that the hydrophile properties of the 'gluconic ac-id salt of the oxyalkylated condensation product in an equal weight of xylene are 'sufiicient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes-of water.

34. The process of claim 16 with "the proviso'that the.

hydrophile properties of the glucon-ic acid' salt of the oxyalkylated condensation product in anequ-al weight or;

xylene are sufliicient to produce an emulsion when said xylene solution -is shaken vigorously with one to three volumes of water. l

'35. The process of claim 17 with the proviso that the hydrophile properties of the 'gluconic acid salt offthe oxy- -alkyla-ted condensation product in an equal weight of xylene are sufiicient to produce an emulsion'when said xylene solution is shaken vigorously with one .to three volumes of water. t

' 36. The process of claim 18 with the proviso that the hydrophile properties of the gluconic acid salt of the oxyalkylated condensation product in an equal weight of xylene are suflicient to produce .anemulsion when said.-

xylene solution is shaken vigorously with one to three volumes, of water.

References Cited in the file of this patent 

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPE CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIER INCLUDING THE GLUCONIC ACID SALTS OF THE BASIC OXYALKYLATED PRODUCTS OBTAINED IN TURN IN THE PROCESS OF CONDENSING (A) AN OXYALKYLATION-SUSCEPTIBEL, FUSIBLE, NON-OXYGENATED ORGANIC SOLVENT-SOLUBLE, WATER-INSOLUBLE, LOW-STAGE PHENOL-ALDEHYDE RESIN HAVING AN AVERAGE MOLECULAR WEIGHT CORRESPONDING TO AT LEAST 3 AND NOT OVER 6 PHENOLIC NUCLEI PER RESIN MOLECULE; SAID RESIN BEING DIFUNCTIONAL ONLY IN REGARD TO METHYLOL-FORMING REACTIVITY; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF TRIFUNCTIONAL PHENOLS; SAID PHENOL BEING OF THE FORMULA 